Directional Activation of Oxygen by the Au-Loaded ZnAl-LDH with Defect Structure for Highly Efficient Photocatalytic Oxidative Coupling of Methane.

Abstract

Photocatalytic oxidative coupling of CH4 (OCM) is a promising CH4 conversion process that can achieve efficient methane conversion with the assistance of O2. It remains to be highly challenging to improve the photocatalytic OCM activity from catalyst design and to deepen the understanding of the reactant activation in the OCM process. In this work, the Au-loaded ZnAl-layered double hydroxides (LDHs) with and without oxygen vacancy are constructed (denoted as Au/ZnAl and Au/ZnAl-v), respectively. When applied for photocatalytic OCM, the Au/ZnAl-v shows a CH4 conversion rate of 8.5 mmol g-1 h-1 with 92% selectivity of C2H6 at 40°C, outperforming most reported photocatalytic OCM systems at low temperature reported in the literature. Furthermore, the catalytic performance of Au/ZnAl-v can be stable for 100h. In contrast, the An/ZnAl exhibits a CH4 conversion rate of 0.8 mmol g-1 h-1 with 46% selectivity of C2H6. Detailed characterizations and DFT calculation studies reveal that the introduced Ov sites on Au/ZnAl-v are able to activate O2, and the resulting superoxide radical O2·- greatly promotes the activation of CH4. The coupling of CH3· groups with the assistance of Au cocatalyst leads to the formation of C2H6 with high photocatalytic activity.